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The full structural characterization of these oxides may be complicated by the presence of support material and lack of a pure bulk phase. For the first time, we show that highly active MnO<jats:sub><jats:italic>x<\/jats:italic><\/jats:sub> catalysts form without supports in situ under photocatalytic conditions. Our most active <jats:sup>4<\/jats:sup>MnO<jats:sub><jats:italic>x<\/jats:italic><\/jats:sub> catalyst (\u223c0.84\u2005mmol\u2009O<jats:sub>2<\/jats:sub>\u2009mol\u2009Mn<jats:sup>\u22121<\/jats:sup>\u2009s<jats:sup>\u22121<\/jats:sup>) forms from a Mn<jats:sub>4<\/jats:sub>O<jats:sub>4<\/jats:sub> bearing a metal\u2013organic framework. <jats:sup>4<\/jats:sup>MnO<jats:sub><jats:italic>x<\/jats:italic><\/jats:sub> is characterized by pair distribution function analysis (PDF), Raman spectroscopy, and HR\u2010TEM as a disordered, layered Mn\u2010oxide with high surface area (216\u2005m<jats:sup>2<\/jats:sup>g<jats:sup>\u22121<\/jats:sup>) and small regions of crystallinity and layer flexibility. In contrast, the <jats:sup>S<\/jats:sup>MnO<jats:sub><jats:italic>x<\/jats:italic><\/jats:sub> formed from Mn<jats:sup>2+<\/jats:sup> salt gives an amorphous species of lower surface area (80\u2005m<jats:sup>2<\/jats:sup>g<jats:sup>\u22121<\/jats:sup>) and lower activity (\u223c0.15\u2005mmol\u2009O<jats:sub>2<\/jats:sub>\u2009mol\u2009Mn<jats:sup>\u22121<\/jats:sup>\u2009s<jats:sup>\u22121<\/jats:sup>). We compare these catalysts to crystalline hexagonal birnessite, which activates under the same conditions. Full deconvolution of the XPS Mn2p<jats:sub>3\/2<\/jats:sub> core levels detects enriched Mn<jats:sup>3+<\/jats:sup> and Mn<jats:sup>2+<\/jats:sup> content on the surfaces, which indicates possible disproportionation\/comproportionation surface equilibria.<\/jats:p>","DOI":"10.1002\/chem.201501930","type":"journal-article","created":{"date-parts":[[2015,8,11]],"date-time":"2015-08-11T09:17:02Z","timestamp":1439284622000},"page":"14218-14228","source":"Crossref","is-referenced-by-count":37,"title":["Surface and Structural Investigation of a MnO<sub><i>x<\/i><\/sub> Birnessite\u2010Type Water Oxidation Catalyst Formed under Photocatalytic Conditions"],"prefix":"10.1002","volume":"21","author":[{"given":"Benjamin J.","family":"Deibert","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jingming","family":"Zhang","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Paul F.","family":"Smith","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Karena W.","family":"Chapman","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sylvie","family":"Rangan","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Debasis","family":"Banerjee","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Kui","family":"Tan","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hao","family":"Wang","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Nicholas","family":"Pasquale","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Feng","family":"Chen","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ki\u2010Bum","family":"Lee","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"G. 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